Zeolite CIT-5 and method of making

ABSTRACT

The present invention relates to new crystalline zeolite CIT-5 prepared using a N(16) methylsparteinium cation templating agent.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new crystalline zeolite CIT-5, a methodfor preparing CIT-5 using a N(16) methylsparteinium cation templatingagent, and processes employing CIT-5 as a catalyst.

2. State of the Art

Because of their unique sieving characteristics, as well as theircatalytic properties, crystalline molecular sieves and zeolites areespecially useful in applications such as hydrocarbon conversion, gasdrying and separation. Although many different crystalline molecularsieves have been disclosed, there is a continuing need for new zeoliteswith desirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New zeolites may containnovel internal pore architectures, providing enhanced selectivities inthese processes.

SUMMARY OF THE INVENTION

The present invention is directed to a family of crystalline molecularsieves with unique properties, referred to herein as "zeolite CIT-5"orsimply "CIT-5". Preferably, CIT-5 is obtained in its silicate oraluminosilicate form. The term "silicate" refers to a zeolite having ahigh mole ratio of silicon oxide relative to aluminum oxide, preferablya mole ratio greater than about 100. As used herein, the term"aluminosilicate" refers to a zeolite containing both alumina andsilica.

In accordance with this invention, there is also provided a zeolitehaving a mole ratio of at least about 100 of an oxide of a tetravalentelement or mixture of oxides of tetravalent elements to an oxide of atrivalent element or mixture of oxides of trivalent elements and having,after calcination, the X-ray diffraction lines of Table II.

Further, in accordance with this invention, there is provided a zeolitehaving a mole ratio of at least about 100 of an oxide selected fromsilicon oxide, germanium oxide and mixtures thereof to an oxide selectedfrom aluminum oxide, boron oxide, gallium oxide and mixtures thereof andhaving, after calcination, the X-ray diffraction lines of Table IIbelow.

The present invention further provides such a zeolite having acomposition, as synthesized and in the anhydrous state, in terms of moleratios as follows:

    ______________________________________                                               YO.sub.2 /W.sub.2 O.sub.3                                                             >100                                                             M/YO.sub.2 ≦0.05                                                       Q/YO.sub.2 ≦0.05                                                     ______________________________________                                    

wherein Y is silicon, germanium or a mixture thereof; W is aluminum,boron, gallium or mixtures thereof; M is lithium or a mixture of lithiumwith another alkali metal; and Q comprises a N(16) methylsparteiniumcation.

In accordance with this invention, there is also provided a zeoliteprepared by thermally treating a zeolite having a mole ratio of an oxideselected from silicon oxide, germanium oxide and mixtures thereof to anoxide selected from aluminum oxide, boron oxide, gallium oxide andmixtures thereof of at least about 100 at a temperature of from about200° C. to about 800° C., the thus-prepared zeolite having the X-raydiffraction lines of Table II. The present invention also includes thisthus-prepared zeolite which is predominantly in the hydrogen form, whichhydrogen form is prepared by ion exchanging with an acid or with asolution of an ammonium salt followed by a second calcination.

Also provided in accordance with the present invention is a method ofpreparing a crystalline material comprising an oxide of a tetravalentelement or mixture of oxides of tetravalent elements and an oxide of atrivalent element or mixture of oxides of trivalent elements, saidmethod comprising contacting in admixture under crystallizationconditions sources of said oxides, a source of lithium and a templatingagent comprising a N(16) methylsparteinium cation.

The present invention additionally provides a process for convertinghydrocarbons comprising contacting a hydrocarbonaceous feed athydrocarbon converting conditions with a catalyst comprising the zeoliteof this invention. The zeolite may be predominantly in the hydrogenform, partially acidic or substantially free of acidity, depending onthe process.

Further provided by the present invention is a hydrocracking processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form.

This invention also includes a dewaxing process comprising contacting ahydrocarbon feedstock under dewaxing conditions with a catalystcomprising the zeolite of this invention, preferably predominantly inthe hydrogen form.

The present invention also includes a process for improving theviscosity index of a dewaxed product of waxy hydrocarbon feedscomprising contacting the waxy hydrocarbon feed under isomerizationdewaxing conditions with a catalyst comprising the zeolite of thisinvention, preferably predominantly in the hydrogen form.

The present invention further includes a process for producing a C₂₀₊lube oil from a C₂₀₊ olefin feed comprising isomerizing said olefin feedunder isomerization conditions over a catalyst comprising at least oneGroup VIII metal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

In accordance with this invention, there is also provided a process forcatalytically dewaxing a hydrocarbon oil feedstock boiling above about350° F. and containing straight chain and slightly branched chainhydrocarbons comprising contacting said hydrocarbon oil feedstock in thepresence of added hydrogen gas at a hydrogen pressure of about 15-3000psi with a catalyst comprising at least one Group VIII metal and thezeolite of this invention, preferably predominantly in the hydrogenform. The catalyst may be a layered catalyst comprising a first layercomprising at least one Group VIII metal and the zeolite of thisinvention, and a second layer comprising an aluminosilicate zeolitewhich is more shape selective than the zeolite of said first layer.

Also included in the present invention is a process for preparing alubricating oil which comprises hydrocracking in a hydrocracking zone ahydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400° F. and at apressure of from about 15 psig to about 3000 psig in the presence ofadded hydrogen gas with a catalyst comprising at least one Group VIIImetal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

Further included in this invention is a process for isomerizationdewaxing a raffinate comprising contacting said raffinate in thepresence of added hydrogen with a catalyst comprising at least one GroupVIII metal and the zeolite of this invention. The raffinate may bebright stock, and the zeolite may be predominantly in the hydrogen form.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content comprising contacting a hydrocarbonaceous feedstockwhich comprises normal and slightly branched hydrocarbons having aboiling range above about 40° C. and less than about 200° C., underaromatic conversion conditions with a catalyst comprising the zeolite ofthis invention made substantially free of acidity by neutralizing saidzeolite with a basic metal. Also provided in this invention is such aprocess wherein the zeolite contains a Group VIII metal component.

Also provided by the present invention is a catalytic cracking processcomprising contacting a hydrocarbon feedstock in a reaction zone undercatalytic cracking conditions in the absence of added hydrogen with acatalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. Also included in this invention issuch a catalytic cracking process wherein the catalyst additionallycomprises a large pore crystalline cracking component.

This invention further provides an isomerization process for isomerizingC₄ to C₇ hydrocarbons, comprising contacting a feed having normal andslightly branched C₄ to C₇ hydrocarbons under isomerizing conditionswith a catalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. The zeolite may be impregnated withat least one Group VIII metal, preferably platinum. The catalyst may becalcined in a steam/air mixture at an elevated temperature afterimpregnation of the Group VIII metal.

Also provided by the present invention is a process for alkylating anaromatic hydrocarbon which comprises contacting under alkylationconditions at least a molar excess of an aromatic hydrocarbon with a C₂to C₂₀ olefin under at least partial liquid phase conditions and in thepresence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The olefin may be a C₂ toC₄ olefin, and the aromatic hydrocarbon and olefin may be present in amolar ratio of about 4:1 to about 20:1, respectively. The aromatichydrocarbon may be selected from the group consisting of benzene,toluene, ethylbenzene, xylene, or mixtures thereof.

Further provided in accordance with this invention is a process fortransalkylating an aromatic hydrocarbon which comprises contacting undertransalkylating conditions an aromatic hydrocarbon with a polyalkylaromatic hydrocarbon under at least partial liquid phase conditions andin the presence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The aromatic hydrocarbonand the polyalkyl aromatic hydrocarbon may be present in a molar ratioof from about 1:1 to about 25:1, respectively. The aromatic hydrocarbonmay be selected from the group consisting of benzene, toluene,ethylbenzene, xylene, or mixtures thereof, and the polyalkyl aromatichydrocarbon may be a dialkylbenzene.

Further provided by this invention is a process to convert paraffins toaromatics which comprises contacting paraffins under conditions whichcause paraffins to convert to aromatics with a catalyst comprising thezeolite of this invention, said catalyst comprising gallium, zinc, or acompound of gallium or zinc.

In accordance with this invention there is also provided a process forisomerizing olefins comprising contacting said olefin under conditionswhich cause isomerization of the olefin with a catalyst comprising thezeolite of this invention.

Further provided in accordance with this invention is a process forisomerizing an isomerization feed comprising an aromatic C₈ stream ofxylene isomers or mixtures of xylene isomers and ethylbenzene, wherein amore nearly equilibrium ratio of ortho-, meta- and para-xylenes isobtained, said process comprising contacting said feed underisomerization conditions with a catalyst comprising the zeolite of thisinvention.

The present invention further provides a process for oligomerizingolefins comprising contacting an olefin feed under oligomerizationconditions with a catalyst comprising the zeolite of this invention.

This invention also provides a process for converting lower alcohols andother oxygenated hydrocarbons comprising contacting said lower alcoholor other oxygenated hydrocarbon with a catalyst comprising the zeoliteof this invention under conditions to produce liquid products.

Also provided by the present invention is an improved process for thereduction of oxides of nitrogen contained in a gas stream in thepresence of oxygen wherein said process comprises contacting the gasstream with a zeolite, the improvement comprising using as the zeolite azeolite having a mole ratio of at least about 100 of an oxide of atetravalent element to an oxide of a trivalent element, divalent elementor mixture thereof and having, after calcination, the X-ray diffractionlines of Table II. The zeolite may contain a metal or metal ions (suchas cobalt, copper or mixtures thereof) capable of catalyzing thereduction of the oxides of nitrogen, and may be conducted in thepresence of a stoichiometric excess of oxygen. In a preferredembodiment, the gas stream is the exhaust stream of an internalcombustion engine.

DETAILED DESCRIPTION OF THE INVENTION

In preparing CIT-5 zeolites, a N(16) methylsparteinium cation is used asa crystallization template. The N(16) methylsparteinium cation may havethe following structure: ##STR1## The anion (X⁻) associated with thecation may be any anion which is not detrimental to the formation of thezeolite. Representative anions include halogen, e.g., fluoride,chloride, bromide and iodide, hydroxide, acetate, sulfate,tetrafluoroborate, carboxylate, and the like. Hydroxide is the mostpreferred anion.

The N(16) methylsparteinium cation may be prepared as described in Loboand Davis, "Synthesis and Characterization of Pure-Silica andBoron-Substituted SSZ-24 Using N(16) methylsparteinium Bromide asStructure-Directing Agent", Microporous Materials 3 (1994), pp. 61-69,Elsevier.

In general, CIT-5 is prepared by contacting an active source of one ormore oxides selected from the group consisting of lithium oxide or amixture of lithium oxide and another alkali metal oxide, trivalentelement oxide(s), and tetravalent element oxide(s) with the N(16)methylsparteinium cation templating agent.

CIT-5 is prepared from a reaction mixture having the composition shownin Table A below.

                  TABLE A                                                         ______________________________________                                        Reaction Mixture                                                                            Typical      Preferred (*)                                      ______________________________________                                        YO.sub.2 /W.sub.2 O.sub.3                                                                     15-∞   25-∞                                         OH-/YO.sub.2  0.1-0.5  0.2-0.45 (0.3)                                         Q/YO.sub.2  0.1-0.3 0.15-0.25 (0.2)                                           M/YO.sub.2 0.02-0.3 0.05-0.2 (0.1)                                            H.sub.2 O/YO.sub.2   15-200   30-100 (40)                                   ______________________________________                                         *Numbers in parentheses represent quantitites believed to be optimal.    

where Y, W, M and Q are as defined above.

In practice, CIT-5 is prepared by a process comprising:

(a) preparing an aqueous solution containing sources of at least oneoxide capable of forming a crystalline molecular sieve and a N(16)methylsparteinium cation having an anionic counterion which is notdetrimental to the formation of CIT-5;

(b) maintaining the aqueous solution under conditions sufficient to formcrystals of CIT-5; and

(c) recovering the crystals of CIT-5.

Accordingly, CIT-5 may comprise the crystalline material and thetemplating agent in combination with metallic and non-metallic oxidesbonded in tetrahedral coordination through shared oxygen atoms to form across-linked three dimensional crystal structure. The metallic andnon-metallic oxides comprise one or a combination of oxides of atetravalent element(s), and, optionally, one or a combination of atrivalent element(s), divalent element(s) or mixture thereof. Thetetravalent element(s) is preferably selected from the group consistingof silicon, germanium and combinations thereof More preferably, thetetravalent element is silicon. The trivalent element is preferablyaluminum, boron or gallium, more preferably aluminum.

Typical sources of aluminum oxide for the reaction mixture includealuminates, alumina, aluminum colloids, aluminum oxide coated on silicasol, hydrated alumina gels such as Al(OH)₃ and aluminum compounds suchas AlCl₃ and Al₂ (SO₄)₃. Typical sources of silicon oxide includesilicates, silica hydrogel, silicic acid, fumed silica, colloidalsilica, tetra-alkyl orthosilicates, and silica hydroxides.

A source zeolite reagent may provide a source of aluminum. In mostcases, the source zeolite also provides a source of silica. The sourcezeolite in its dealuminated or form may also be used as a source ofsilica, with additional silicon added using, for example, theconventional sources listed above. Use of a source zeolite reagent as asource of alumina for the present process is more completely describedin U.S. Pat. No. 5,225,179, issued Jul. 6, 1993 to Zones et al. entitled"Method of Making Molecular Sieves", the disclosure of which isincorporated herein by reference.

Lithium or a mixture of lithium and another alkali metal is added to thereaction mixture. A variety of lithium sources can be used, such aslithium hydroxide and lithium carbonate, with lithium hydroxide beingpreferred. The lithium cation may be part of the as-synthesizedcrystalline oxide material, in order to balance valence electron chargestherein. Other alkali metals which can be used in combination with thelithium include sodium and potassium, with the hydroxides beingpreferred. The lithium may be employed in an amount of from about 0.03to about 0.15 mole of lithium per mole of silica (or other oxide(s) of atetravalent element(s)).

It has been found that the inclusion of zinc in the reaction mixture canhelp prevent the formation of crystal phases other than the CIT-5. Thezinc can be added as, e.g., zinc acetate dihydrate, in an amount of upto about 0.08, preferably about 0.04, mole of zinc acetate dihydrate permole of silica (or other oxide(s) of a tetravalent element(s)).

The reaction mixture is maintained at an elevated temperature until thecrystals of the CIT-5 zeolite are formed. The hydrothermalcrystallization is usually conducted under autogenous pressure, at atemperature between 100° C. and 200° C., preferably between 135° C. and160° C. The crystallization period is typically greater than 1 day andpreferably from about 7 days to about 21 days.

During the hydrothermal crystallization step, the CIT-5 crystals can beallowed to nucleate spontaneously from the reaction mixture. The use ofCIT-5 crystals as seed material can be advantageous in decreasing thetime necessary for complete crystallization to occur. In addition,seeding can lead to an increased purity of the product obtained bypromoting the nucleation and/or formation of CIT-5 over any undesiredphases. When used as seeds, CIT-5 crystals are added in an amountbetween 0.1 and 10% of the weight of silica used in the reactionmixture.

Once the zeolite crystals have formed, the solid product is separatedfrom the reaction mixture by standard mechanical separation techniquessuch as filtration. The crystals are water-washed and then dried, e.g.,at 90° C. to 150° C. for from 8 to 24 hours, to obtain theas-synthesized CIT-5 zeolite crystals. The drying step can be performedat atmospheric pressure or under vacuum.

CIT-5 has a composition, as synthesized and in the anhydrous state, interms of mole ratios, shown in Table B below.

                  TABLE B                                                         ______________________________________                                        As-Synthesized CIT-5                                                          ______________________________________                                               YO.sub.2 /W.sub.2 O.sub.3                                                             >100                                                             M/YO.sub.2 ≦0.05                                                       Q/YO.sub.2 ≦0.05                                                     ______________________________________                                    

where Y, W, M and Q are as defined above.

Lower silica to alumina ratios may also be obtained by using methodswhich insert aluminum into the crystalline framework. For example,aluminum insertion may occur by thermal treatment of the zeolite incombination with an alumina binder or dissolved source of alumina. Suchprocedures are described in U.S. Patent No. 4,559,315, issued on Dec.17, 1985 to Chang et al.

It is believed that CIT-5 is comprised of a new framework structure ortopology which is characterized by its X-ray diffraction pattern. CIT-5zeolites, as-synthesized, have a crystalline structure whose X-raypowder diffraction pattern typically exhibits the characteristic linesshown in Table I and are thereby distinguished from other knownzeolites.

                  TABLE I                                                         ______________________________________                                        As-Synthesized All-Silica CIT-5                                                 2 Theta.sup.(a) d      Relative Intensity.sup.(b)                           ______________________________________                                         6.96         12.7   VS                                                          7.29 12.12 S                                                                 12.81 6.905 W                                                                 13.93 6.353 M                                                                 18.96 4.676 S                                                                 19.59 4.528 M                                                                 20.00 4.436 S                                                                 20.50 4.329 M-S                                                               20.95 4.236 S-VS                                                              21.93 4.050 W                                                                 23.41 3.797 W                                                                 24.22 3.672 W                                                                 24.62 3.612 M                                                                 25.80 3.451 W                                                                 26.10 3.412 W                                                                 26.73 3.332 S-VS                                                              27.11 3.286 W                                                                 28.22 3.159 M                                                                 29.38 3.038 W                                                                 29.82 2.994 W                                                                 31.37 2.849 W                                                                 31.55 2.833 W                                                                 32.99 2.713 W                                                                 33.98 2.636 W                                                                 35.33 2.538 W                                                                 35.64 2.517 W                                                                 36.42 2.465 W                                                                 37.03 2.426 W                                                                 37.70 2.384 W                                                                 38.73 2.323 W                                                                 44.70 2.026 W                                                                 49.42 1.843 W                                                               ______________________________________                                         .sup.(a) ±0.15                                                             .sup.(b) The Xray patterns provided are based on a relative intensity         scale in which the strongest line in the Xray pattern is assigned a value     of 100: W(weak) is less than 20; M(medium) is between 20 and 40; S(strong     is between 40 and 60; VS(very strong) is greater than 60.                

After calcination, the CIT-5 zeolites have a crystalline structure whoseX-ray powder diffraction pattern typically includes the characteristiclines shown in Table II:

                  TABLE II                                                        ______________________________________                                        Calcined CIT-5                                                                  2 Theta.sup.(a)  d      Relative Intensity                                  ______________________________________                                        6.95           12.7   VS                                                        7.3 12.1 S-VS                                                                 13.9 6.37 W-S                                                                 19.0 4.67 W-VS                                                                20.0 4.44 M-VS                                                                20.5 4.33 W-S                                                                 20.9 4.25 W-VS                                                                24.6 3.62 W-M                                                                 26.8 3.32 W-VS                                                              ______________________________________                                         .sup.(a) ±0.15                                                        

Table IIA below shows the X-ray powder diffraction lines for calcinedCIT-5 including actual relative intensities.

                  TABLE IIA                                                       ______________________________________                                        Calcined CIT-5                                                                  2 Theta.sup.(a)  d      Relative Intensity                                  ______________________________________                                        6.95           12.7   65-100                                                    7.3 12.1 40-100                                                               13.9 6.37 1-65                                                                19.0 4.67 10-100                                                              20.0 4.44 20-70                                                               20.5 4.33 10-50                                                               20.9 4.25  5-100                                                              24.6 3.62 5-45                                                                26.8 3.32 10-70                                                             ______________________________________                                         .sup.(a) ±0.15                                                        

The X-ray powder diffraction patterns were determined by standardtechniques. The radiation was the K-alpha/doublet of copper. The peakheights and the positions, as a function of 2θ where θ is the Braggangle, were read from the relative intensities of the peaks, and d, theinterplanar spacing in Angstroms corresponding to the recorded lines,can be calculated.

The variation in the scattering angle (two theta) measurements, due toinstrument error and to differences between individual samples, isestimated at ± degrees.

The X-ray diffraction pattern of Table I is representative of"as-synthesized" or "as-made" CIT-5 zeolites. Minor variations in thediffraction pattern can result from variations in the, e.g.,silica-to-alumina mole ratio of the particular sample due to changes inlattice constants. In addition, sufficiently small crystals will affectthe shape and intensity of peaks, leading to significant peakbroadening.

Representative peaks from the X-ray diffraction pattern of calcinedCIT-5 are shown in Table II. Calcination can also result in changes inthe intensities of the peaks as compared to patterns of the "as-made"material, as well as minor shifts in the diffraction pattern. Thezeolite produced by exchanging the metal or other cations present in thezeolite with various other cations (such as H⁺ or NH₄ ⁺) yieldsessentially the same diffraction pattern, although again, there may beminor shifts in the interplanar spacing and variations in the relativeintensities of the peaks. Notwithstanding these minor perturbations, thebasic crystal lattice remains unchanged by these treatments.

Crystalline CIT-5 can be used as-synthesized, but preferably will bethermally treated (calcined). Usually, it is desirable to remove thealkali metal cation by ion exchange and replace it with hydrogen,ammonium, or any desired metal ion. The zeolite can be leached withchelating agents, e.g., EDTA or dilute acid solutions, to increase thesilica to alumina mole ratio. The zeolite can also be steamed; steaminghelps stabilize the crystalline lattice to attack from acids.

The zeolite can be used in intimate combination with hydrogenatingcomponents, such as tungsten, vanadium molybdenum, rhenium, nickelcobalt, chromium, manganese, or a noble metal, such as palladium orplatinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

Metals may also be introduced into the zeolite by replacing some of thecations in the zeolite with metal cations via standard ion exchangetechniques (see, for example, U.S. Pat. No. 3,140,249 issued Jul. 7,1964 to Plank et al.; U.S. Pat. No. 3,140,251 issued Jul. 7, 1964 toPlank et al.; and U.S. Pat. No. 3,140,253 issued Jul. 7, 1964 to Planket al.). Typical replacing cations can include metal cations, e.g., rareearth, Group IA, Group IIA and Group VIII metals, as well as theirmixtures. Of the replacing metallic cations, cations of metals such asrare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe areparticularly preferred.

The hydrogen, ammonium, and metal components can be ion-exchanged intothe CIT-5. The zeolite can also be impregnated with the metals, or, themetals can be physically and intimately admixed with the zeolite usingstandard methods known to the art.

Typical ion-exchange techniques involve contacting the synthetic zeolitewith a solution containing a salt of the desired replacing cation orcations. Although a wide variety of salts can be employed, chlorides andother halides, acetates, nitrates, and sulfates are particularlypreferred. The zeolite is usually calcined prior to the ion-exchangeprocedure to remove the organic matter present in the channels and onthe surface, since this results in a more effective ion exchange.Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. No. 3,140,249 issued on Jul. 7, 1964 toPlank et al.; U.S. Pat. No. 3,140,251 issued on Jul. 7, 1964 to Plank etal.; and U.S. Pat. No. 3,140,253 issued on Jul. 7, 1964 to Plank et al.

Following contact with the salt solution of the desired replacingcation, the zeolite is typically washed with water and dried attemperatures ranging from 65° C. to about 200° C. After washing, thezeolite can be calcined in air or inert gas at temperatures ranging fromabout 200° C. to about 800° C. for periods of time ranging from 1 to 48hours, or more, to produce a catalytically active product especiallyuseful in hydrocarbon conversion processes.

Regardless of the cations present in the synthesized form of CIT-5, thespatial arrangement of the atoms which form the basic crystal lattice ofthe zeolite remains essentially unchanged.

CIT-5 can be formed into a wide variety of physical shapes. Generallyspeaking, the zeolite can be in the form of a powder, a granule, or amolded product, such as extrudate having a particle size sufficient topass through a 2-mesh (Tyler) screen and be retained on a 400-mesh(Tyler) screen. In cases where the catalyst is molded, such as byextrusion with an organic binder, the aluminosilicate can be extrudedbefore drying, or, dried or partially dried and then extruded.

CIT-5 can be composited with other materials resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Pat.No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which areincorporated by reference herein in their entirety.

Hydrocarbon Conversion Processes

CIT-5 zeolites are useful in hydrocarbon conversion reactions.Hydrocarbon conversion reactions are chemical and catalytic processes inwhich carbon containing compounds are changed to different carboncontaining compounds. Examples of hydrocarbon conversion reactions inwhich CIT-5 are expected to be useful include hydrocracking, dewaxing,catalytic cracking and olefin and aromatics formation reactions. Thecatalysts are also expected to be useful in other petroleum refining andhydrocarbon conversion reactions such as isomerizing n-paraffins andnaphthenes, polymerizing and oligomerizing olefinic or acetyleniccompounds such as isobutylene and butene-1, reforming, isomerizingpolyalkyl substituted aromatics (e.g., m-xylene), and disproportionatingaromatics (e.g., toluene) to provide mixtures of benzene, xylenes andhigher methylbenzenes and oxidation reactions. Also included arerearrangement reactions to make various naphthalene derivatives. TheCIT-5 catalysts may have high selectivity, and under hydrocarbonconversion conditions can provide a high percentage of desired productsrelative to total products.

CIT-5 zeolites can be used in processing hydrocarbonaceous feedstocks.Hydrocarbonaceous feedstocks contain carbon compounds and can be frommany different sources, such as virgin petroleum fractions, recyclepetroleum fractions, shale oil, liquefied coal, tar sand oil, syntheticparaffins from NAO, recycled plastic feedstocks and, in general, can beany carbon containing feedstock susceptible to zeolitic catalyticreactions. Depending on the type of processing the hydrocarbonaceousfeed is to undergo, the feed can contain metal or be free of metals, itcan also have high or low nitrogen or sulfur impurities. It can beappreciated, however, that in general processing will be more efficient(and the catalyst more active) the lower the metal, nitrogen, and sulfurcontent of the feedstock.

The conversion of hydrocarbonaceous feeds can take place in anyconvenient mode, for example, in fluidized bed, moving bed, or fixed bedreactors depending on the types of process desired. The formulation ofthe catalyst particles will vary depending on the conversion process andmethod of operation.

Other reactions which can be performed using the catalyst of thisinvention containing a metal, e.g., a Group VIII metal such platinum,include hydrogenation-dehydrogenation reactions, denitrogenation anddesulfurization reactions.

Depending upon the type of reaction which is catalyzed, the zeolite maybe predominantly in the hydrogen form, partially acidic or substantiallyfree of acidity. As used herein, "predominantly in the hydrogen form"means that, after calcination, at least 80% of the cation sites areoccupied by hydrogen ions and/or rare earth ions.

The following table indicates typical reaction conditions which may beemployed when using catalysts comprising CIT-5 in the hydrocarbonconversion reactions of this invention. Preferred conditions areindicated in parentheses.

    ______________________________________                                        Process    Temp., ° C.                                                                       Pressure     LHSV                                       ______________________________________                                        Hydrocracking                                                                            175-485    0.5-350 bar  0.1-30                                       Dewaxing 200-475 15-3000 psig 0.1-20                                           (250-450) (200-3000) (0.2-10)                                                Aromatics 400-600 atm.-10 bar 0.1-15                                          formation (480-550)                                                           Cat. cracking 127-885 subatm.-.sup.1 0.5-50                                     (atm.-5 atm.)                                                               Oligomerization 232-649.sup.2 0.1-50 atm..sup.2,3 0.2-50.sup.2                  10-232.sup.4 -- 0.05-20.sup.5                                                 (27-204).sup.4 -- (0.1-10).sup.5                                            Paraffins to 100-700 0-1000 psig 0.5-40.sup.5                                 aromatics                                                                     Condensation of 260-538 0.5-1000 psig 0.5-50.sup.5                            alcohols                                                                      Isomerization  93-538 50-1000 psig 1-10                                        (204-315)  (1-4)                                                             Xylene  260-593.sup.2 0.5-50 atm..sup.2 0.1-100.sup.5                         isomerization  (315-566).sup.2 (1-5 atm) (0.5-50).sup.5                         38-371.sup.4 1-200 atm..sup.4 0.5-50                                      ______________________________________                                         .sup.1 Several hundred atmospheres                                            .sup.2 Gas phase reaction                                                     .sup.3 Hydrocarbon partial pressure                                           .sup.4 Liquid phase reaction                                                  .sup.5 WHSV                                                              

Other reaction conditions and parameters are provided below.

Hydrocracking

Using a catalyst which comprises CIT-5, preferably predominantly in thehydrogen form, and a hydrogenation promoter, heavy petroleum residualfeedstocks, cyclic stocks and other hydrocrackate charge stocks can behydrocracked using the process conditions and catalyst componentsdisclosed in the aforementioned U.S. Pat. No. 4,910,006 and U.S. Pat.No. 5,316,753.

The hydrocracking catalysts contain an effective amount of at least onehydrogenation component of the type commonly employed in hydrocrackingcatalysts. The hydrogenation component is generally selected from thegroup of hydrogenation catalysts consisting of one or more metals ofGroup VIB and Group VIII, including the salts, complexes and solutionscontaining such. The hydrogenation catalyst is preferably selected fromthe group of metals, salts and complexes thereof of the group consistingof at least one of platinum, palladium, rhodium, iridium, ruthenium andmixtures thereof or the group consisting of at least one of nickel,molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof.Reference to the catalytically active metal or metals is intended toencompass such metal or metals in the elemental state or in some formsuch as an oxide, sulfide, halide, carboxylate and the like. Thehydrogenation catalyst is present in an effective amount to provide thehydrogenation function of the hydrocracking catalyst, and preferably inthe range of from 0.05 to 25% by weight.

Dewaxing

CIT-5, preferably predominantly in the hydrogen form, can be used todewax hydrocarbonaceous feeds by selectively removing straight chainparaffins. Typically, the viscosity index of the dewaxed product isimproved (compared to the waxy feed) when the waxy feed is contactedwith CIT-5 under isomerization dewaxing conditions.

The catalytic dewaxing conditions are dependent in large measure on thefeed used and upon the desired pour point. Hydrogen is preferablypresent in the reaction zone during the catalytic dewaxing process. Thehydrogen to feed ratio is typically between about 500 and about 30,000SCF/bbl (standard cubic feet per barrel), preferably about 1000 to about20,000 SCF/bbl. Generally, hydrogen will be separated from the productand recycled to the reaction zone. Typical feedstocks include light gasoil, heavy gas oils and reduced crudes boiling above about 350° F.

A typical dewaxing process is the catalytic dewaxing of a hydrocarbonoil feedstock boiling above about 350° F. and containing straight chainand slightly branched chain hydrocarbons by contacting the hydrocarbonoil feedstock in the presence of added hydrogen gas at a hydrogenpressure of about 15-3000 psi with a catalyst comprising CIT-5 and atleast one Group VIII metal.

The CIT-5 hydrodewaxing catalyst may optionally contain a hydrogenationcomponent of the type commonly employed in dewaxing catalysts. See theaforementioned U.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 forexamples of these hydrogenation components.

The hydrogenation component is present in an effective amount to providean effective hydrodewaxing and hydroisomerization catalyst preferably inthe range of from about 0.05 to 5% by weight. The catalyst may be run insuch a mode to increase isodewaxing at the expense of crackingreactions.

The feed may be hydrocracked, followed by dewaxing. This type of twostage process and typical hydrocracking conditions are described in U.S.Pat. No. 4,921,594, issued May 1, 1990 to Miller, which is incorporatedherein by reference in its entirety.

CIT-5 may also be utilized as a dewaxing catalyst in the form of alayered catalyst. That is, the catalyst comprises a first layercomprising zeolite CIT-5 and at least one Group VIII metal, and a secondlayer comprising an aluminosilicate zeolite which is more shapeselective than zeolite CIT-5. The use of layered catalysts is disclosedin U.S. Pat. No. 5,149,421, issued Sep. 22, 1992 to Miller, which isincorporated by reference herein in its entirety. The layering may alsoinclude a bed of CIT-5 layered with a non-zeolitic component designedfor either hydrocracking or hydrofinishing.

CIT-5 may also be used to dewax raffinates, including bright stock,under conditions such as those disclosed in U.S. Pat. No. 4,181,598,issued Jan. 1, 1980 to Gillespie et al., which is incorporated byreference herein in its entirety.

It is often desirable to use mild hydrogenation (sometimes referred toas hydrofinishing) to produce more stable dewaxed products. Thehydrofinishing step can be performed either before or after the dewaxingstep, and preferably after. Hydrofinishing is typically conducted attemperatures ranging from about 190° C. to about 340° C. at pressuresfrom about 400 psig to about 3000 psig at space velocities (LHSV)between about 0.1 and 20 and a hydrogen recycle rate of about 400 to1500 SCF/bbl. The hydrogenation catalyst employed must be active enoughnot only to hydrogenate the olefins, diolefins and color bodies whichmay be present, but also to reduce the aromatic content. Suitablehydrogenation catalyst are disclosed in U.S. Pat. No. 4,921,594, issuedMay 1, 1990 to Miller, which is incorporated by reference herein in itsentirety. The hydrofinishing step is beneficial in preparing anacceptably stable product (e.g., a lubricating oil) since dewaxedproducts prepared from hydrocracked stocks tend to be unstable to airand light and tend to form sludges spontaneously and quickly.

Lube oil may be prepared using CIT-5. For example, a C₂₀₊ lube oil maybe made by isomerizing a C₂₀₊ olefin feed over a catalyst comprisingCIT-5 in the hydrogen form and at least one Group VIII metal.Alternatively, the lubricating oil may be made by hydrocracking in ahydrocracking zone a hydrocarbonaceous feedstock to obtain an effluentcomprising a hydrocracked oil, and catalytically dewaxing the effluentat a temperature of at least about 400° F. and at a pressure of fromabout 15 psig to about 3000 psig in the presence of added hydrogen gaswith a catalyst comprising CIT-5 in the hydrogen form and at least oneGroup VIII metal.

Aromatics Formation

CIT-5 can be used to convert light straight run naphthas and similarmixtures to highly aromatic mixtures. Thus, normal and slightly branchedchained hydrocarbons, preferably having a boiling range above about 40°C. and less than about 200° C., can be converted to products having asubstantial higher octane aromatics content by contacting thehydrocarbon feed with a catalyst comprising CIT-5. It is also possibleto convert heavier feeds into BTX or naphthalene derivatives of valueusing a catalyst comprising CIT-5.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium or tin or amixture thereof may also be used in conjunction with the Group VIIImetal compound and preferably a noble metal compound. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inreforming catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

It is critical to the selective production of aromatics in usefulquantities that the conversion catalyst be substantially free ofacidity, for example, by neutralizing the zeolite with a basic metal,e.g., alkali metal, compound. Methods for rendering the catalyst free ofacidity are known in the art. See the aforementioned U.S. Pat. No.4,910,006 and U.S. Pat. No. 5,316,753 for a description of such methods.

The preferred alkali metals are sodium, potassium, rubidium and cesium.The zeolite itself can be substantially free of acidity only at veryhigh silica:alumina mole ratios.

Catalytic Cracking

Hydrocarbon cracking stocks can be catalytically cracked in the absenceof hydrogen using CIT-5, preferably predominantly in the hydrogen form.

When CIT-5 is used as a catalytic cracking catalyst in the absence ofhydrogen, the catalyst may be employed in conjunction with traditionalcracking catalysts, e.g., any aluminosilicate heretofore employed as acomponent in cracking catalysts. Typically, these are large pore,crystalline aluminosilicates. Examples of these traditional crackingcatalysts are disclosed in the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No 5,316,753. When a traditional cracking catalyst (TC)component is employed, the relative weight ratio of the TC to the CIT-5is generally between about 1:10 and about 500:1, desirably between about1:10 and about 200:1, preferably between about 1:2 and about 50:1, andmost preferably is between about 1:1 and about 20:1. The novel zeoliteand/or the traditional cracking component may be further ion exchangedwith rare earth ions to modify selectivity.

The cracking catalysts are typically employed with an inorganic oxidematrix component. See the aforementioned U.S. Pat. No. 4,910,006 andU.S. Pat. No. 5,316,753 for examples of such matrix components.

Isomerization

The present catalyst, preferably predominantly in the hydrogen form, isbelieved to be active and selective for isomerizing C₄ to C₇hydrocarbons. The activity means that the catalyst can operate atrelatively low temperature which thermodynamically favors highlybranched paraffins. Consequently, the catalyst can produce a high octaneproduct. The selectivity means that a relatively high liquid yield canbe achieved when the catalyst is run at a high octane.

The present process comprises contacting the isomerization catalyst,i.e., a catalyst comprising CIT-5 in the hydrogen form, with ahydrocarbon feed under isomerization conditions. The feed is preferablya light straight run fraction, boiling within the range of 30° F. to250° F. and preferably from 60° F. to 200° F. Preferably, thehydrocarbon feed for the process comprises a substantial amount of C₄ toC₇ normal and slightly branched low octane hydrocarbons, more preferablyC₅ and C₆ hydrocarbons.

It is preferable to carry out the isomerization reaction in the presenceof hydrogen. Preferably, hydrogen is added to give a hydrogen tohydrocarbon ratio (H₂ /HC) of between 0.5 and 10 H₂ /HC, more preferablybetween 1 and 8 H₂ /HC. See the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No. 5,316,753 for a further discussion of isomerizationprocess conditions.

A low sulfur feed is especially preferred in the present process. Thefeed preferably contains less than 10 ppm, more preferably less than 1ppm, and most preferably less than 0.1 ppm sulfur. In the case of a feedwhich is not already low in sulfur, acceptable levels can be reached byhydrogenating the feed in a presaturation zone with a hydrogenatingcatalyst which is resistant to sulfur poisoning. See the aforementionedU.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 for a furtherdiscussion of this hydrodesulfurization process.

It is preferable to limit the nitrogen level and the water content ofthe feed. Catalysts and processes which are suitable for these purposesare known to those skilled in the art.

After a period of operation, the catalyst can become deactivated bysulfur or coke. See the aforementioned U.S. Pat. No. 4,910,006 and U.S.Pat. No. 5,316,753 for a further discussion of methods of removing thissulfur and coke, and of regenerating the catalyst.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium and tin mayalso be used in conjunction with the noble metal. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inisomerizing catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

Alkylation and Transalkylation

CIT-5 can be used in a process for the alkylation or transalkylation ofan aromatic hydrocarbon. The process comprises contacting the aromatichydrocarbon with a C₂ to C₁₆ olefin alkylating agent or a polyalkylaromatic hydrocarbon transalkylating agent, under at least partialliquid phase conditions, and in the presence of a catalyst comprisingCIT-5.

CIT-5 can also be used for removing benzene from gasoline by alkylatingthe benzene as described above and removing the alkylated product fromthe gasoline.

For high catalytic activity, the CIT-5 zeolite should be predominantlyin its hydrogen ion form. It is preferred that, after calcination, atleast 80% of the cation sites are occupied by hydrogen ions and/or rareearth ions.

Examples of suitable aromatic hydrocarbon feedstocks which may bealkylated or transalkylated by the process of the invention includearomatic compounds such as benzene, toluene and xylene. The preferredaromatic hydrocarbon is benzene. There may be occasions wherenaphthalene derivatives may be desirable. Mixtures of aromatichydrocarbons may also be employed.

Suitable olefins for the alkylation of the aromatic hydrocarbon arethose containing 2 to 20, preferably 2 to 4, carbon atoms, such asethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, ormixtures thereof. There may be instances where pentenes are desirable.The preferred olefins are ethylene and propylene. Longer chain alphaolefins may be used as well.

When transalkylation is desired, the transalkylating agent is apolyalkyl aromatic hydrocarbon containing two or more alkyl groups thateach may have from 2 to about 4 carbon atoms. For example, suitablepolyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkylaromatic hydrocarbons, such as diethylbenzene, triethylbenzene,diethylmethylbenzene (diethyltoluene), di-isopropylbenzene,di-isopropyltoluene, dibutylbenzene, and the like. Preferred polyalkylaromatic hydrocarbons are the dialkyl benzenes. A particularly preferredpolyalkyl aromatic hydrocarbon is di-isopropylbenzene.

When alkylation is the process conducted, reaction conditions are asfollows. The aromatic hydrocarbon feed should be present instoichiometric excess. It is preferred that molar ratio of aromatics toolefins be greater than four-to-one to prevent rapid catalyst fouling.The reaction temperature may range from 100° F. to 600° F., preferably250° F. to 450° F. The reaction pressure should be sufficient tomaintain at least a partial liquid phase in order to retard catalystfouling. This is typically 50 psig to 1000 psig depending on thefeedstock and reaction temperature. Contact time may range from 10seconds to 10 hours, but is usually from 5 minutes to an hour. Theweight hourly space velocity (WHSV), in terms of grams (pounds) ofaromatic hydrocarbon and olefin per gram (pound) of catalyst per hour,is generally within the range of about 0.5 to 50.

When transalkylation is the process conducted, the molar ratio ofaromatic hydrocarbon will generally range from about 1:1 to 25:1, andpreferably from about 2:1 to 20:1. The reaction temperature may rangefrom about 100° F. to 600° F., but it is preferably about 250° F. to450° F. The reaction pressure should be sufficient to maintain at leasta partial liquid phase, typically in the range of about 50 psig to 1000psig, preferably 300 psig to 600 psig. The weight hourly space velocitywill range from about 0.1 to 10. U.S. Pat. No. 5,082,990 issued on Jan.21, 1992 to Hsieh, et al. describes such processes and is incorporatedherein by reference.

Isomerization of Olefins

CIT-5 can be used to isomerize olefins. The feed stream is a hydrocarbonstream containing at least one C₄₋₆ olefin, preferably a C₄₋₆ normalolefin, more preferably normal butene. Normal butene as used in thisspecification means all forms of normal butene, e.g., 1-butene,cis-2-butene, and trans-2-butene. Typically, hydrocarbons other thannormal butene or other C₄₋₆ normal olefins will be present in the feedstream. These other hydrocarbons may include, e.g., alkanes, otherolefins, aromatics, hydrogen, and inert gases.

The feed stream typically may be the effluent from a fluid catalyticcracking unit or a methyl-tert-butyl ether unit. A fluid catalyticcracking unit effluent typically contains about 40-60 weight percentnormal butenes. A methyl-tert-butyl ether unit effluent typicallycontains 40-100 weight percent normal butene. The feed stream preferablycontains at least about 40 weight percent normal butene, more preferablyat least about 65 weight percent normal butene. The terms iso-olefin andmethyl branched iso-olefin may be used interchangeably in thisspecification.

The process is carried out under isomerization conditions. Thehydrocarbon feed is contacted in a vapor phase with a catalystcomprising the CIT-S. The process may be carried out generally at atemperature from about 625° F. to about 950° F. (329-510° C.), forbutenes, preferably from about 700° F. to about 900° F. (371-482° C.),and about 350° F. to about 650° F. (177-343° C.) for pentenes andhexenes. The pressure ranges from subatmospheric to about 200 psig,preferably from about 15 psig to about 200 psig, and more preferablyfrom about 1 psig to about 150 psig.

The liquid hourly space velocity during contacting is generally fromabout 0.1 to about 50 hr⁻¹, based on the hydrocarbon feed, preferablyfrom about 0.1 to about 20 hr⁻¹ , more preferably from about 0.2 toabout 10 hr⁻¹, most preferably from about 1 to about 5 hr⁻¹. Ahydrogen/hydrocarbon molar ratio is maintained from about 0 to about 30or higher. The hydrogen can be added directly to the feed stream ordirectly to the isomerization zone. The reaction is preferablysubstantially free of water, typically less than about two weightpercent based on the feed. The process can be carried out in a packedbed reactor, a fixed bed, fluidized bed reactor, or a moving bedreactor. The bed of the catalyst can move upward or downward. The molepercent conversion of, e.g., normal butene to iso-butene is at least 10,preferably at least 25, and more preferably at least 35.

Conversion of Paraffins to Aromatics

CIT-5 can be used to convert light gas C₂ -C₆ paraffins to highermolecular weight hydrocarbons including aromatic compounds. Preferably,the zeolite will contain a catalyst metal or metal oxide wherein saidmetal is selected from the group consisting of Groups IB, IIB, VIII andIIIA of the Periodic Table. Preferably, the metal is gallium, niobium,indium or zinc in the range of from about 0.05 to 5% by weight.

Xylene Isomerization

CIT-5 may also be useful in a process for isomerizing one or more xyleneisomers in a C₈ aromatic feed to obtain ortho-, meta-, and para-xylenein a ratio approaching the equilibrium value. In particular, xyleneisomerization is used in conjunction with a separate process tomanufacture para-xylene. For example, a portion of the para-xylene in amixed C₈ aromatics stream may be recovered by crystallization andcentrifugation. The mother liquor from the crystallizer is then reactedunder xylene isomerization conditions to restore ortho-, meta- andpara-xylenes to a near equilibrium ratio. At the same time, part of theethylbenzene in the mother liquor is converted to xylenes or to productswhich are easily separated by filtration. The isomerate is blended withfresh feed and the combined stream is distilled to remove heavy andlight by-products. The resultant C₈ aromatics stream is then sent to thecrystallizer to repeat the cycle.

Optionally, isomerization in the vapor phase is conducted in thepresence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene(e.g., ethylbenzene). If hydrogen is used, the catalyst should compriseabout 0.1 to 2.0 wt % of a hydrogenation/dehydrogenation componentselected from Group VIII (of the Periodic Table) metal component,especially platinum or nickel. By Group VIII metal component is meantthe metals and their compounds such as oxides and sulfides.

Optionally, the isomerization feed may contain 10 to 90 wt % of adiluent such as toluene, trimethylbenzene, naphthenes or paraffins.

Oligomerization

It is expected that CIT-5 can also be used to oligomerize straight andbranched chain olefins having from about 2 to 21 and preferably 2-5carbon atoms. The oligomers which are the products of the process aremedium to heavy olefins which are useful for both fuels, i.e., gasolineor a gasoline blending stock and chemicals.

The oligomerization process comprises contacting the olefin feedstock inthe gaseous or liquid phase with a catalyst comprising CIT-5.

The zeolite can have the original cations associated therewith replacedby a wide variety of other cations according to techniques well known inthe art. Typical cations would include hydrogen, ammonium and metalcations including mixtures of the same. Of the replacing metalliccations, particular preference is given to cations of metals such asrare earth metals, manganese, calcium, as well as metals of Group II ofthe Periodic Table, e.g., zinc, and Group VIII of the Periodic Table,e.g., nickel. One of the prime requisites is that the zeolite have afairly low aromatization activity, i.e., in which the amount ofaromatics produced is not more than about 20% by weight. This isaccomplished by using a zeolite with controlled acid activity [alphavalue] of from about 0.1 to about 120, preferably from about 0.1 toabout 100, as measured by its ability to crack n-hexane.

Alpha values are defined by a standard test known in the art, e.g., asshown in U.S. Pat. No. 3,960,978 issued on Jun. 1, 1976 to Givens et al.which is incorporated totally herein by reference. If required, suchzeolites may be obtained by steaming, by use in a conversion process orby any other method which may occur to one skilled in this art.

Condensation of Alcohols

CIT-5 can be used to condense lower aliphatic alcohols having 1 to 10carbon atoms to a gasoline boiling point hydrocarbon product comprisingmixed aliphatic and aromatic hydrocarbon. The process disclosed in U.S.Pat. No. 3,894,107, issued Jul. 8, 1975 to Butter et al., describes theprocess conditions used in this process, which patent is incorporatedtotally herein by reference.

The catalyst may be in the hydrogen form or may be base exchanged orimpregnated to contain ammonium or a metal cation complement, preferablyin the range of from about 0.05 to 5% by weight. The metal cations thatmay be present include any of the metals of the Groups I through VIII ofthe Periodic Table. However, in the case of Group IA metals, the cationcontent should in no case be so large as to effectively inactivate thecatalyst, nor should the exchange be such as to eliminate all acidity.There may be other processes involving treatment of oxygenatedsubstrates where a basic catalyst is desired.

Other Uses for CIT-5

CIT-5 can also be used as an adsorbent with high selectivities based onmolecular sieve behavior and also based upon preferential hydrocarbonpacking within the pores.

CIT-5 may also be used for the catalytic reduction of the oxides ofnitrogen in a gas stream. Typically, the gas stream also containsoxygen, often a stoichiometric excess thereof. Also, the CIT-5 maycontain a metal or metal ions within or on it which are capable ofcatalyzing the reduction of the nitrogen oxides. Examples of such metalsor metal ions include copper, cobalt and mixtures thereof.

One example of such a process for the catalytic reduction of oxides ofnitrogen in the presence of a zeolite is disclosed in U.S. Pat. No.4,297,328, issued Oct. 27, 1981 to Ritscher et al., which isincorporated by reference herein. There, the catalytic process is thecombustion of carbon monoxide and hydrocarbons and the catalyticreduction of the oxides of nitrogen contained in a gas stream, such asthe exhaust gas from an internal combustion engine. The zeolite used ismetal ion-exchanged, doped or loaded sufficiently so as to provide aneffective amount of catalytic copper metal or copper ions within or onthe zeolite. In addition, the process is conducted in an excess ofoxidant, e.g., oxygen.

EXAMPLES

The following examples demonstrate but do not limit the presentinvention.

Example 1 Synthesis of N(16) Methylsparteinium Hydroxide (MeSPAOH)

21.1 Grams (50 mmol) of (-) sparteine sulfate pentahydrate (Aldrich) isadded to 50 ml of a 3 M NaOH solution. The resulting suspension isstirred until the crystals are completely dissolved and two phases form.The organic phase is extracted three times with 25 ml portions ofdiethyl ether and the combined extracts are dried over solid KOH (85%)and filtered. The solvent is then evaporated at room temperature undervacuum. The recovered (-) sparteine is dissolved in 100 ml of acetonecontaining 28.3 g (1.5 equiv.) of methyl iodide. The resulting reactionmixture is stirred in the dark for 24 hours. and the yellow solidproduct which forms is filtered after the addition of 50 ml of diethylether. The recovered solid (15.2 g, 81% yield) is recrystallized twicein 2-propanol by adding ethyl acetate until turbidity to give 13.7 g(73% yield) of slightly yellow crystals. Analyses: Calculated for C₁₆ N₂H₂₉ I: C, 51.1%; N, 7.4%; H, 7.7%; 1, 33.8%. Found: C, 51.0%; N, 7.4%;H, 7.9%; I,33.7%. The IR spectrum of the product agrees with apreviously reported spectrum for N(16) methylsparteinium iodide.

Amberlite IRA-400(Cl) (Aldrich) anion exchange resin, exchanged to thebromide form, is used to convert the iodide salt prepared as above tothe corresponding bromide. Typically, 7.52 g of N(16) methylsparteiniumiodide (20 mmol) is dissolved in 50 ml of water and exchanged in an ionexchange column containing 100 ml of anion exchange resin (with 140 mmolof exchange capacity). After washing the column with an additional 200ml of distilled water, the aqueous solution obtained is evaporated in arotavapor until dryness and recrystallized as described above from2-propanol-ethyl acetate. Elemental analyses indicate a yield of 95% forthe bromide form. Similarly, the hydroxide form is obtained usingAmberlite IRA-400 (OH) anion exchange resin. After exchange, the aqueoussolution is concentrated to 50 ml. The yield is 92.8% based on titrationof the resultant solution and gives a concentration of 0.371 M of N(16)methylsparteinium hydroxide.

Example 2 Preparation of Silicate CIT-5

0.018 Gram of LiOH anhydrous powder is dissolved in 2.54 g of distilledwater. To the resulting solution is added 2.21 g of N(16)methylsparteinium hydroxide (MeSPAOH) solution (18.2 wt %) and theresulting reaction mixture is stirred for 10 minutes. SiO₂ (Ludox HS-30from E. I. duPont), 1.5 g, is added to the reaction mixture and themixture is stirred for two hours. The resulting gel is divided intoportions and heated in three quartz tubes at 175° C. for 7 days, 10 daysand 11 days at autogenous pressure. The product is recovered by vacuumfiltration and determined by X-ray diffraction (XRD) to be CIT-5 (theproduct recovered after 10 days also contains some amorphous material).

Typical XRD lines for the as-made (i.e., uncalcined) product of thisexample is indicated in Table III below.

                  TABLE III                                                       ______________________________________                                        2 Theta        d       I/I.sub.2  × 100                                 ______________________________________                                         6.957         12.695  77                                                        7.288 12.119 50                                                              12.810 6.905 4                                                                13.929 6.353 37                                                               17.093 5.183 3                                                                18.963 4.676 100                                                              19.588 4.529 25                                                               20.001 4.436 57                                                               20.499 4.329 40                                                               20.953 4.236 60                                                               21.770 4.079 3                                                                21.931 4.050 8                                                                22.613 3.929 7                                                                23.410 3.797 13                                                               24.218 3.672 6                                                                24.625 3.612 34                                                               25.796 3.451 5                                                                26.097 3.412 7                                                                26.733 3.332 59                                                               27.116 3.286 18                                                               28.224 3.159 28                                                               29.378 3.038 4                                                                29.818 2.994 6                                                                31.374 2.849 11                                                               31.550 2.833 4                                                                32.990 2.713 6                                                                33.980 2.636 5                                                                35.330 2.539 4                                                                35.636 2.517 10                                                               36.417 2.465 7                                                                37.027 2.426 5                                                                37.700 2.384 4                                                                38.731 2.323 4                                                                44.699 2.026 11                                                               49.424 1.843 4                                                              ______________________________________                                    

Example 3 Synthesis of CIT-5 in the Presence of Zinc

In a manner similar to that described in Example 2, CIT-5 is made fromthe following components:

0.012 g LiOH

1.70 g distilled water

1.47 g MeSPAOH solution (18.2 wt %)

0.043 g Zn(CH₃ COO)₂ 2H₂ O

1.0 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.1 LiOH: 0.04 Zn(CH₃ COO)₂ 2H₂ O: 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered by vacuum filtration after 13 days and 15 days, anddetermined by XRD to be CIT-5 (the product recovered after 15 days alsocontains some unknown material).

Typical XRD lines for the as-made product of this example is indicatedin Table IV below.

                  TABLE IV                                                        ______________________________________                                        2 Theta        d       I/I.sub.2  × 100                                 ______________________________________                                         6.903         12.794  17                                                        7.268 12.152 43                                                              12.001 7.368 7                                                                12.846 6.886 5                                                                13.841 6.393 9                                                                14.597 6.064 3                                                                16.331 5.423 34                                                               18.930 4.684 61                                                               19.641 4.516 40                                                               19.967 4.443 58                                                               20.432 4.343 40                                                               20.826 4.262 21                                                               21.590 4.113 30                                                               21.963 4.044 18                                                               23.348 3.807 8                                                                24.208 3.674 3                                                                24.548 3.623 20                                                               25.878 3.440 11                                                               26.799 3.324 100                                                              27.146 3.282 23                                                               28.129 3.170 25                                                               29.964 2.990 3                                                                30.209 2.958 2                                                                31.276 2.853 6                                                                31.625 2.827 3                                                                32.913 2.719 4                                                                33.462 2.676 5                                                                33.719 2.656 4                                                                35.569 2.522 20                                                               36.265 2.475 8                                                                37.051 2.424 6                                                                37.848 2.375 5                                                                38.646 2.328 3                                                                44.625 2.029 4                                                                44.828 2.020 6                                                                47.102 1.928 4                                                                49.616 1.836 5                                                              ______________________________________                                    

After the product is calcined, it has the XRD lines indicated in Table Vbelow.

                  TABLE V                                                         ______________________________________                                        2 Theta        d       I/I.sub.2  × 100                                 ______________________________________                                         6.913         12.777  39                                                        7.305 12.092 100                                                             12.224 7.235 7                                                                12.921 6.846 13                                                               13.830 6.398 --                                                               13.917 6.358 --                                                               18.995 4.668 41                                                               19.754 4.491 21                                                               20.044 4.426 60                                                               20.503 4.328 47                                                               20.864 4.254 17                                                               21.295 4.169 10                                                               21.645 4.102 28                                                               22.103 4.018 10                                                               22.568 3.937 2                                                                23.409 3.797 6                                                                24.319 3.657 7                                                                24.612 3.614 13                                                               26.016 3.422 7                                                                26.172 3.402 3                                                                26.944 3.306 57                                                               27.282 3.266 16                                                               28.059 3.178 6                                                                28.222 3.160 18                                                               29.910 2.985 3                                                                30.254 2.952 1                                                                31.393 2.847 5                                                                31.778 2.814 1                                                                33.020 2.710 4                                                                33.589 2.666 2                                                                33.876 2.644 0                                                                34.358 2.608 1                                                                35.702 2.513 21                                                               36.289 2.474 3                                                                36.427 2.465 6                                                                37.233 2.413 5                                                                38.024 2.365 3                                                                38.807 2.319 1                                                                43.680 2.070 2                                                                44.596 2.030 1                                                                45.017 2.012 4                                                                45.921 1.975 1                                                                47.293 1.921 3                                                                48.250 1.885 0                                                                48.846 1.863 0                                                                49.869 1.827 3                                                                50.537 1.805 3                                                              ______________________________________                                    

Example 4 Synthesis of Aluminosilicate CIT-5

In a manner similar to that described in Example 2, aluminosilicateCIT-5 is made from the following components:

0.018 g LiOH

3.47 g distilled water

1.27 g MeSPAOH solution (31.0 wt %)

0.028 g Al(NO₃)₃.9H₂ O

1.50 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.1 LiOH: 0.01 Al(NO₃)₃.9H₂ O: 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered by vacuum filtration after 7 days and 9 days, anddetermined by XRD to be CIT-5.

Typical XRD lines for the as-made product of this example is indicatedin Table VI below.

                  TABLE VI                                                        ______________________________________                                        2 Theta        d       I/I.sub.2  × 100                                 ______________________________________                                         6.334         13.942  3                                                         7.000 12.617 100                                                             7.287 12.122 25                                                               12.650 6.992 2                                                                12.825 6.897 3                                                                13.010 6.799 2                                                                13.361 6.621 2                                                                13.972 6.333 58                                                               14.590 6.066 3                                                                18.170 4.878 3                                                                18.323 4.838 3                                                                18.992 4.669 73                                                               19.599 4.526 18                                                               20.032 4.429 41                                                               20.523 4.324 31                                                               20.996 4.228 99                                                               21.800 4.074 3                                                                21.981 4.041 6                                                                23.447 3.791 9                                                                24.251 3.667 5                                                                24.655 3.608 31                                                               25.393 3.505 4                                                                25.802 3.450 3                                                                26.104 3.411 4                                                                26.749 3.330 45                                                               27.148 3.282 13                                                               28.130 3.170 22                                                               28.234 3.158 23                                                               29.836 2.992 3                                                                31.374 2.849 8                                                                33.065 2.707 4                                                                33.481 2.674 4                                                                35.308 2.540 3                                                                35.675 2.515 8                                                                36.492 2.460 7                                                                37.007 2.427 4                                                                37.744 2.382 4                                                                38.796 2.319 3                                                                44.750 2.024 9                                                                47.198 1.924 3                                                                49.639 1.835 2                                                              ______________________________________                                    

After the product is calcined, it has the XRD lines indicated in TableVII below.

                  TABLE VII                                                       ______________________________________                                        2 Theta        d       I/I.sub.2  × 100                                 ______________________________________                                         6.922         12.760  100                                                       7.301 12.098  86                                                             12.235 7.228 11                                                               12.920 6.847 6                                                                13.869 6.380 7                                                                17.105 5.180 --                                                               17.161 5.163 1                                                                18.515 4.788 1                                                                18.989 4.670 40                                                               19.730 4.496 11                                                               20.041 4.427 31                                                               20.510 4.327 26                                                               20.876 4.252 26                                                               23.437 3.793 5                                                                24.301 3.660 4                                                                24.613 3.614 18                                                               25.235 3.526 2                                                                26.008 3.423 3                                                                26.147 3.405 4                                                                26.923 3.309 29                                                               27.268 3.268 8                                                                27.947 3.190 4                                                                28.222 3.160 16                                                               29.887 2.987 1                                                                30.223 2.955 1                                                                31.367 2.850 5                                                                31.796 2.812 1                                                                32.232 2.775 1                                                                33.010 2.711 3                                                                33.563 2.668 2                                                                33.849 2.646 1                                                                34.345 2.609 1                                                                35.152 2.551 --                                                               35.690 2.514 7                                                                36.337 2.470 4                                                                37.208 2.415 3                                                                37.591 2.391 1                                                                38.018 2.365 2                                                                38.757 2.322 1                                                                39.350 2.288 --                                                               40.031 2.251 --                                                               40.782 2.211 --                                                               41.103 2.194 --                                                               41.957 2.152 --                                                               42.892 2.107 1                                                                43.694 2.070 1                                                                44.581 2.031 2                                                                44.997 2.013 2                                                                45.937 1.974 1                                                                47.281 1.921 2                                                                48.265 1.884 --                                                               48.863 1.862 --                                                               49.857 1.828 2                                                                50.562 1.804 3                                                              ______________________________________                                    

Example 5 Synthesis of Aluminosilicate CIT-5

In a manner similar to that described in Example 2, aluminosilicateCIT-5 is made from the following components:

0.18 g LiOH

3.47 g distilled water

1.27 g MeSPAOH solution (31.0 wt %)

0.048 g Al(NO₃)₃.9H₂ O

1.5 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.1 LiOH: 0.02 Al(NO₃)₃ : 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered after 21 days and determined by XRD to be a mixtureof amorphous material and CIT-5.

Comparative Example A Attempted Synthesis of Aluminosilicate CIT-5

In a manner similar to that described in Example 2, aluminosilicateCIT-5 is made from the following components:

0.18 g LiOH

3.35 g distilled water

1.27 g MeSPAOH solution (31.0 wt %)

0.281 g Al(NO₃)₃.9H₂ O

1.5 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.1 LiOH: 0.1 Al(NO₃)₃ : 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered after 60 days and determined by XRD to be amorphousmaterial.

Example 6 Synthesis of Borosilicate CIT-5

In a manner similar to that described in Example 2, borosilicate CIT-5is made from the following components:

0.18 g LiOH

3.47 g distilled water

1.27 g MeSPAOH solution (31.0 wt %)

0.0046 g H₃ BO₃

1.5 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.1 LiOH: 0.01 H₃ BO₃ : 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered after 7 days and determined by XRD to be CIT-5.

Example 7 Synthesis of Gallosilicate CIT-5

In a manner similar to that described in Example 2, gallosilicate CIT-5is made from the following components:

0.18 g LiOH

3.47 g distilled water

1.27 g MeSPAOH solution (31.0 wt %)

0.019 g Ga(NO₃)₃.xH₂ O (x=3.4)

1.5 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.1 LiOH: 0.01 Ga(NO₃)₃ : 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered after 7 days and determined by XRD to be CIT-5.

Example 8 Synthesis of Silicate CIT-5

In a manner similar to that described in Example 2, silicate CIT-5 issynthesized in a Teflon lined autoclave instead of quartz tubes from thefollowing components:

0.18 g LiOH

4.22 g distilled water

0.86 g MeSPAOH solution (49.8 wt %)

1.6 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.1 LiOH: 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered after 6 days and determined by XRD to be CIT-5.

Example 9 Synthesis of Silicate CIT-5 Using Li and Na

In a manner similar to that described in Example 8, silicate CIT-5 issynthesized from the following components:

0.14 g LiOH

0.016 g 50 wt % aqueous NaOH solution

4.22 g distilled water

0.86 g MeSPAOH solution (49.8 wt %)

1.6 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.075 LiOH: 0.025 NaOH: 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered after 5 days and determined by XRD to be CIT-5.

Example 10 Synthesis of Silicate CIT-5 Using Li and K

In a manner similar to that described in Example 8, silicate CIT-5 issynthesized from the following components:

0.14 g LiOH

0.022 g 50 wt % aqueous KOH solution

4.22 g distilled water

0.86 g MeSPAOH solution (49.8 wt %)

1.6 g SiO₂ (Ludox HS-30)

This produces a gel composition, in terms of mole ratios, as follows:

0.075 LiOH: 0.025 KOH: 0.2 MeSPAOH: SiO₂ : 40 H₂ O

Product is recovered after 5 days and determined by XRD to be CIT-5 andamorphous material.

Example 11 Synthesis of Aluminosilicate CIT-5

In the Teflon cup for a small Parr reactor is combined 3.4 grams of a0.66 M solution of MeSPAOH template with 8.5 grams of water and 0.06gram of lithium carbonate. 0.90 Gram of 390-HUA Y zeolite (sold byTosoh) is added as a source of both silicon and aluminum. The reactor issealed and heated at 160° C. while being tumbled at 43 RPM for a periodof 12 days. Upon cooling the reactor, the solid product is collected byfiltration, washed and dried. The product is determined by XRD to beCIT-5.

The CIT-5 product is calcined and ammonium ion exchanged as previouslydescribed.

Example 12 Preparation of Pd CIT-5

0.99 Gram of the ammonium exchanged CIT-5 prepared in Example 11 isslurried into 9 ml of water and 2 ml of a 0.156 N ammonium hydroxidesolution. A solution of palladium tetraamine dinitrate buffered inammonium hydroxide is then added. The quantity of palladium issufficient to provide 0.50 wt % Pd on the CIT-5 if completely ionexchanged onto the zeolite. The zeolite and solution are allowed tostand for several days at room temperature, after which the zeolite isfiltered and washed. This product is then calcined at 482° C. after aslow ramp to 120° C. followed by a 1 degree C/minute increase to 482° C.The zeolite is held at 482° C. for three hours.

Example 13 Hydrocracking and Hydroisomerization of n-Hexane Using PdCIT-5

0.50 Gram of the Pd CIT-5 prepared in Example 12 is pressed into atablet at 3000 psi, fractured, meshed to 20-40, and loaded into astainless steel reactor. The zeolite is dried in situ and the reactortemperature is brought to 600° F. (315° C.) and pressurized to 1200 psihydrogen flow. A n-hexadecane feed is introduced at 1.00microliter/minute. At 167 hours on stream and at 660° F. (349° C.), thecatalyst is achieving 96% conversion. The liquid to gas ratio of theconverted products is 5.3. Iso/normal ratios for the gasoline fractionsand hexadecane are given below.

    ______________________________________                                        Carbon No.    Iso/Normal ratio                                                ______________________________________                                        4             1.95                                                              5 3.19                                                                        6 2.89                                                                        7 3.52                                                                        8 4.20                                                                        9 4.69                                                                        10   5.82                                                                     16  7.87                                                                    ______________________________________                                    

Example 14 Adsorption Properties of CIT-5

A sample of silicate CIT-5 from Example 2 (crystallized for 11 days) iscalcined by heating it from room temperature to 700° C. over a period ofthree hours and maintaining it at 700° C. for an additional two hours.The calcined sample's adsorption properties are determined by a McBainBaker balance. The resulting adsorption properties are--cyclohexane:0.07 ml/g 2,2-dimethylpropane: 0.05 ml/g.

Example 15 Reactions of m-Xylene Over CIT-5

CIT-5 with a Si/Al mole ratio of about 200 is pressed into a wafer. Thewafer is then crushed into small pellets. The pellets are size sorted,and only pellets of the size -35/+70 are used. 100-150 Milligrams of thecatalyst is placed in a downward flow reactor. The catalyst ispretreated in a flow of helium at 50 ml/min. with the followingtemperature program:

    ______________________________________                                        2 hr   2 hr       1.5 hr     3 hr                                             ______________________________________                                        RT------>                                                                            175° C.------>                                                                    175° C.------>                                                                    350° C.------>                                                                  350° C.                          ______________________________________                                    

The temperature is the decreased to 317° C. over 25 minutes and thenmaintained at this temperature for the reaction. The helium flow isreduced to 20 ml/min. and directed through a saturator containingm-xylene (Aldrich 99+%) which is kept at 10° C. (+0.5° C.). The vaporpressure of m-xylene at this temperature is 3.4 torr. Thehelium/m-xylene stream is then passed over the catalyst bed forreaction. Products are analyzed with an on-line gas chromatograph. Theresults are indicated below.

Catalyst mass=116.2 mg

Initial conversion=2.5%

Para/Ortho=0.9

Isomerization/Disproportionation=11

Only 1,2,4 trimethylbenzene is formed, although this is likely due tothe low conversion. The 1,3,5 isomer is detected by the gaschromatograph, but the amount of this material is too small to beintegrated by the gas chromatograph's integrator.

What is claimed is:
 1. A zeolite having a mole ratio of at least about100 of an oxide of a tetravalent element or mixture of oxides oftetravalent elements to an oxide of a trivalent element or mixture oftrivalent elements and having, after calcination, the X-ray diffractionlines of Table II.
 2. A zeolite having a mole ratio of at least about100 of an oxide selected from the group consisting of silicon oxide,germanium oxide and mixtures thereof to an oxide selected from aluminumoxide, boron oxide, gallium oxide and mixtures thereof, and having,after calcination, the X-ray diffraction lines of Table II.
 3. A zeoliteaccording to claim 2 wherein the oxides comprise silicon oxide andaluminum oxide.
 4. A zeolite according to claim 2 wherein the oxidescomprise silicon oxide and boron oxide.
 5. A zeolite according to claim2 wherein the oxides comprise silicon oxide and gallium oxide.
 6. Azeolite according to claim 1 wherein said zeolite is predominantly inthe hydrogen form.
 7. A zeolite according to claim 1 wherein saidzeolite is substantially free of acidity.
 8. A zeolite having acomposition, as synthesized and in the anhydrous state, in terms of moleratios as follows:

    ______________________________________                                               YO.sub.2 /W.sub.2 O.sub.3                                                             >100                                                             M/YO.sub.2 ≦0.05                                                       Q/YO.sub.2 ≦0.05                                                     ______________________________________                                    

wherein Y is silicon, germanium or a mixture thereof; W is aluminum,boron, gallium or mixtures thereof; M is lithium or a mixture of lithiumand another alkali metal; and Q comprises a N(16) methylsparteiniumcation, and having, after calcination, the X-ray diffraction lines ofTable II.
 9. A zeolite according to claim 8 wherein W is aluminum and Yis silicon.
 10. A zeolite according to claim 8 wherein W is boron and Yis silicon.
 11. A zeolite according to claim 8 wherein W is gallium andY is silicon.
 12. A method of preparing a crystalline materialcomprising an oxide of a tetravalent element or mixture of oxides oftetravalent elements and an oxide of a trivalent element or mixture ofoxides of trivalent elements, said method comprising contacting inadmixture under crystallization conditions sources of said oxides, asource of lithium and a templating agent comprising a N(16)methylsparteinium cation, and having, after calcination, the X-raydiffraction lines of Table II.
 13. The method according to claim 12wherein the tetravalent element is selected from the group consisting ofsilicon, germanium and combinations thereof.
 14. The method according toclaim 12 wherein the trivalent element is selected from the groupconsisting of aluminum, boron, gallium and mixtures thereof.
 15. Themethod according to claim 12 wherein the tetravalent element is siliconand the trivalent element is aluminum.
 16. The method according to claim12 wherein the tetravalent element is silicon and the trivalent elementis boron.
 17. The method according to claim 12 wherein the tetravalentelement is silicon and the trivalent element is gallium.
 18. The methodof claim 12 wherein the source of lithium contains no alkali metal otherthan lithium.
 19. The method of claim 12 wherein the source of lithiumalso contains another alkali metal.
 20. The method of claim 12 whereinthe admixture further comprises a source of zinc.